U.S. patent number 4,937,016 [Application Number 07/304,631] was granted by the patent office on 1990-06-26 for copper conductor composition.
This patent grant is currently assigned to Dai-Ichi Kogyo Seiyaku Co., Ltd., Dowa Mining Co., Ltd., Matsushita Electric Industrial Co., Ltd.. Invention is credited to Masashi Echigo, Nobutoshi Kawamura, Masami Sakuraba, Masatoshi Suehiro.
United States Patent |
4,937,016 |
Suehiro , et al. |
June 26, 1990 |
**Please see images for:
( Certificate of Correction ) ** |
Copper conductor composition
Abstract
A copper conductor composition comprising a copper powder, an
inorganic oxide powder, a glass powder and an organic vehicle, said
copper powder having an average particle size of 0.5 to 3 .mu.m, a
tap density of 3.0 to 5.0 g/cm.sup.3, and an oxygen content of 0.05
to 0.15% by weight. Zinc oxide powder and, optionally, nickel
powder are used as the inorganic oxide powder. The composition
which contains the copper powder having such an oxygen content as
low as 0.05 to 0.15% by weight, can provide copper conductors
having excellent conductor properties such as solderability,
adhesive strength and matching property to resistances.
Inventors: |
Suehiro; Masatoshi (Kyoto,
JP), Echigo; Masashi (Kyoto, JP), Sakuraba;
Masami (Kyoto, JP), Kawamura; Nobutoshi (Kyoto,
JP) |
Assignee: |
Dai-Ichi Kogyo Seiyaku Co.,
Ltd. (Kyoto, JP)
Dowa Mining Co., Ltd. (Tokyo, JP)
Matsushita Electric Industrial Co., Ltd. (Kadoma,
JP)
|
Family
ID: |
23177315 |
Appl.
No.: |
07/304,631 |
Filed: |
February 1, 1989 |
Current U.S.
Class: |
252/512;
106/1.13; 106/1.29; 252/519.32; 252/519.5 |
Current CPC
Class: |
H05K
1/092 (20130101); H01B 1/16 (20130101) |
Current International
Class: |
H01B
1/14 (20060101); H01B 1/16 (20060101); H05K
1/09 (20060101); H01B 001/06 () |
Field of
Search: |
;252/512,518,519
;106/1.13,1.18,1.22,1.23,1.26,1.29 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Barr; Josephine
Attorney, Agent or Firm: Armstrong, Nikaido, Marmelstein,
Kubovcik & Murray
Claims
What we claim is:
1. A copper conductor composition comprising 100 parts by weight of
a copper powder having an average particle size of 0.5 to 0.3
.mu.m, a tap density of 3.0 to 5.0 g/cm.sup.3 and an oxygen content
of 0.05 to 0.15% by weight; 0.2 to 3 parts by weight of a zinc
oxide powder having an average particle size of 0.5 to 5.mu.m; 0 to
2 parts by weight of a nickel oxide powder having an average
particle size of 0.5 to 5.mu.m; 1 to 10 parts by weight of a glass
powder and 10 to 30 parts by weight of an organic vehicle.
2. The composition of claim 1, wherein said copper powder is
obtained by reducing a cuprous oxide powder with hydrazine to give
a copper powder and then hydrogenating the copper powder.
3. The composition of claim 2, wherein said cuprous oxide powder is
a wet precipitate of a cuprous oxide obtained by reducing a copper
sulfate with glucose in an alkali hydroxide and separating from the
reaction mixture.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a copper-containing conductor
composition, and more particularly to a composition for providing a
copper conductor which is formed into conductor patterns or
electrodes on, mainly, ceramic substrates. The composition of the
present invention can give excellent solderability (wettability by
solder), adhesive strength, migration resistance and solder leach
resistance to the conductor.
Thick film conductor compositions are composed of, generally, a
conductive metal, an inorganic oxide and a glass powder as an
inorganic bonding agent, which are in finely divided form and are
dispersed in an organic vehicle. The conductive metal is ordinarily
gold, silver, palladium, platinum, or mixtures and alloys thereof.
However, these metals are noble metals, and they are expensive and
have large fluctuations in price. When the noble metals other than
gold are used as the conductive metal of the conductor composition,
the obtained conductor has many troubles on its properties, for
instance, high migration, poor solder leach resistance, high
resistivity, and the like.
Accordingly, it has been strongly expected to substitute base
metals, particularly copper metal, which are cheap and have small
fluctuation in price, for the noble metals.
As to copper conductor compositions, hitherto, there have been
utilized as the conductive metal ingredient spherical copper
powders prepared in a wet process, a dry process, a combination
thereof, and the like. However, commercially available copper
powders have an oxide which contains at least 0.2% by weight oxygen
as a copper oxide on the surface. That is, it can be considered
that the copper powder is naturally oxidized during preparation
process thereof or the powder is previously oxidized from the
viewpoint of stability of copper. Since copper is very easily
oxidized in air, even if the copper powder is subjected to
antioxidation treatment, it is oxidized during the treatment to
produce the oxide having at least 0.2% by weight oxygen.
The present inventors prepared various copper conductor
compositions from the above-mentioned conventional copper powders.
As a result, it has been found that the obtained copper conductor,
in any compositions, could not satisfy all of properties required
as conductor (conductor properties) such as solderability, adhesive
strength, matching property to resistance, variation by preparation
lots, due to at least 0.2% by weight oxygen in the oxide on the
surface of the copper powder. On the other hand, when a copper
powder put on the market is washed with an acid such as
hydrochloric acid or nitric acid in order to remove an oxide from
the surface, it can be considered that though the oxide layer on
the surface can be removed therefrom immediately after washing,
since the treated copper powder is remarkably easily oxidized
during drying or storage, the amount of the oxide is consequently
increased compared to the case that the copper is not treated.
An object of the present invention is to provide a copper conductor
composition capable of providing a conductor satisfying all of the
conductor properties.
This and other objects of the present invention will become
apparent from the description hereinafter.
SUMMARY OF THE INVENTION
As to copper conductor compositions having excellent properties and
preparation processes of the copper powder capable of giving
excellent properties to the conductor, the present inventors have
repeated earnest studies. As a result, it has now been found out a
preparation process of stable copper powders which are lower in
oxygen content than the conventional copper powders and found that
the conductor compositions containing the above copper powders
having low oxygen content can provide conductors having the
excellent conductor properties.
In accordance with the present invention, there is provided a
copper conductor composition comprising a copper powder, an
inorganic oxide powder, a glass powder and an organic vehicle; the
copper powder having an average particle size of 0.5 to 3.0 .mu.m,
a tap density of 3.0 to 5.0 g/cm.sup.3 and an oxygen content of
0.05 to 0.15% by weight.
DETAILED DESCRIPTION
The copper conductor composition of the present invention is
characterized by the copper powder having a low oxygen content. In
the invention, as to ingredients other than the copper powder of
the copper conductor composition, any ingredients used usually in
the copper conductor composition can be used without any
limitation. The copper conductor composition of the invention is
composed of the copper powder, an inorganic oxide powder, a glass
powder, an organic vehicle and, if necessary, a dispersing
agent.
In the present invention, the copper powder has an average particle
size of 0.5 to 3.0 .mu.m, preferably from 0.5 to 2.5 .mu.m. When
the average particle size of the copper powder is less than 0.5
.mu.m, it is hard to obtain the composition in the state of a
paste. Even if the composition can be obtained in the state of a
paste, blisters are easily produced during firing. On the other
hand, when the average particle size is more than 3.0 .mu.m, the
conductor properties, particularly adhesive strength, cannot be
improved.
The tap density of the copper powder is from 3.0 to 5.0 g/cm.sup.3,
preferably from 3.5 to 5.0 g/cm.sup.3. The tap density is measured
according to JIS-Z-2504. When the tap density of the copper powder
is less than 3.0 g/cm.sup.3, it is hard to obtain the composition
in the state of a paste. On the other hand, when the tap density is
more than 5.0 g/cm.sup.3, the conductor properties, particularly
adhesive strength and solderability, are poor.
The copper powder used in the copper conductor composition of the
invention is lower in oxygen content than conventionally used
copper powders. That is, in the present invention, the oxygen
content of the copper powder is from 0.05 to 0.15% by weight,
preferably from 0.1 to 0.15% by weight. The oxygen content is
measured by RO 18 type inert gas melt-infrared absorption oxygen
analyzer made by LECO CORPORATION. Such copper powders having low
oxygen content can give excellent sintering property to the
composition to prepare a close conductor film, thus the conductors
having excellent resistivity and solderability can be obtained.
When the oxygen content of the copper powder is less than 0.05% by
weight, the stability of the copper powder is poor, so the copper
powder is easily oxidized during preparation of the paste and the
prepared conductor varies in the properties according to the used
preparation lots. On the other hand when the oxygen content is more
than 0.15% by weight, since the sintering property of the copper
powder is poor, the solderability and adhesive strength become
unsatisfactory. In order to improve the adhesive strength, copper
oxide powder or bismuth oxide powder is generally added to the
copper composition. The addition of copper or bismuth oxide powder
can improve the adhesive strength, but exerts a bad influence on
conductivity and solderability, and further matching property to
resistor become poor.
The copper powder having low oxygen content as used in the
invention can be obtained as follows:
An aqueous solution of a salt of copper, preferably copper sulfate,
is reduced with glucose in the presence of an alkali hydroxide such
as NaOH or KOH to give a reaction mixture containing a precipitate
of a cuprous oxide powder (the first step). Then, the precipitate
of cuprous oxide powder is separated from the reaction mixture by
any separating means such as decantation, centrifugal separation or
filtration. The obtained wet precipitate (squeezing ratio: about 15
to 30% by weight) is dispersed in water as it is, that is, the
separated precipitate is dispersed in water without subjecting to
any treatment such as drying. The aqueous dispersion is reduced
with hydrazine to give a reaction mixture containing a precipitate
of copper powder (the second step). Finally, the precipitate of
copper powder is separated from the reaction mixture by
decantation, centrifugal separation, filtration, and the like. The
obtained precipitate is washed with water, dried and hydrogenated
at a temperature of 150.degree. to 250.degree. C., to give a copper
powder used in the present invention (the third step).
Thus obtained copper powder has the oxygen content of about 0.05 to
0.1% by weight, and even if the copper powder is stored in an
ordinary atmosphere (the atmosphere) for about one month, the
oxygen content of the copper powder reaches to at most 0.15% by
weight.
It can be considered that the reason why thus obtained copper
powder is very stable is that organic matter remaining on the
surface of copper powder inhibits the oxidation of the copper
powder during the hydrogenation (third step). The reason why the
copper powder has the organic matter on its surface is that the
copper powder is obtained by reducing the copper salt with glucose
then reducing the wet precipitate of cuprous oxide with
hydrazine.
In the above-mentioned process for preparing the copper powder, it
is important that glucose is used as the reducing agent in the
first step, the separated wet precipitate is dispersed in water as
it is in the second step, and the third step is conducted, that is,
the obtained copper powder is hydrogenated, in order to obtain the
copper powder having low oxygen content. When one of three
conditions as mentioned above is not satisfied, i.e., when the
reduction of the copper sulfate is conducted by using other
reducing agents than glucose in the first step, the precipitate of
cuprous oxide powder is dried before dispersing in the second step,
or the third step, the hydrogenation of copper powder is omitted,
the oxygen content of the obtained copper powder becomes not less
than 0.2% by weight.
When the copper conductor composition has the copper powder
prepared according to the above-mentioned preparation process, the
obtained composition can provide the copper conductors having
excellent conductor properties such as solderability, adhesive
strength and matching property to resistor.
As the inorganic oxide powder, zinc oxide powder is preferably
used. The amount of the zinc oxide powder is from 0.2 to 3 parts by
weight, preferably from 0.5 to 2 parts by weight, based on 100
parts by weight of the copper powder. When the amount of the zinc
oxide powder is less than 0.2 part by weight based on 100 parts by
weight of the copper powder, the desired adhesive strength cannot
be obtained. On the other hand, when the amount is more than 3
parts by weight, the solderability becomes poor.
In the present invention, the copper conductor composition may
contain nickel oxide powder in addition to zinc oxide powder to
promote adhesive strength. The amount of nickel oxide is, when
adding it, from 0 to 2.0 parts by weight, preferably from 0 to 1.0
part by weight, based on 100 parts by weight of the copper powder,
within the range of the total amount of the inorganic oxide powder
of not more than 3 parts by weight. Although the adhesive strength
is sufficient on practical use even if nickel oxide is not added,
the addition of up to 2 parts by weight of nickel oxide can further
improve the adhesive strength. When the amount of nickel oxide is
more than 2 parts by weight, the solderability becomes poor.
The average particle size of the inorganic oxide powder is from 0.5
to 5 .mu.m, preferably from 1 to 3 .mu.m.
Examples of the glass powders are, for instance, borate glasses
such as lead borate glass, borosilicate glasses such as lead
borosilicate glass and zinc borosilicate glass, and the like. The
glass powder may be used alone or as an admixture thereof. The
amount of the glass powder is from 1 to 10 parts by weight,
preferably from 2 to 8 parts by weight, based on 100 parts by
weight of the copper powder.
The average particle size of the glass powder is from 0.5 to 10
.mu.m, preferably from 1 to 5 .mu.m.
Usually used organic vehicles in the copper conductor composition
are applicable to the present invention without particular
limitation. Examples of the organic vehicles are, for instance, a
solvent such as an aliphatic alcohol, an ester of aliphatic
alcohol, e.g., acetate or propionate of an aliphatic alcohol, a
terpene e.g. wood turpentine oil, a terpineol; a solution wherein a
resin such as a polymethacrylate of lower alcohol or ethyl
cellulose is dissolved in the above-mentioned solvent; and the
like.
The composition of the present invention may contain other
additives such as a dispersing agent. As each ingredient of the
composition except the copper powder of the present invention,
goods on the market may be used.
The copper conductor composition is composed of 100 parts by weight
of the copper powder having an average particle size of 0.5 to 3.0
.mu.m, a tap density of 3.0 to 5.0 g/cm.sup.3 and an oxygen content
of 0.05 to 0.15% by weight; 0.2 to 3 parts by weight, preferably
from 0.5 to 2.0 parts by weight of zinc oxide powder and 0 to 2.0
parts by weight of nickel oxide powder; 1 to 10 parts by weight,
preferably from 2 to 8 parts by weight, of the glass powder and 10
to 30 parts by weight, preferably from 10 to 20 parts by weight, of
the organic vehicle.
As the substrate in the invention, the alumina ceramic substrates
are used and also the beryllia ceramic substrates can be used.
The copper conductor composition is prepared by kneading the copper
powder, the inorganic oxide powder and the glass powder with the
organic vehicle to disperse the inorganic ingredients in the
organic vehicle. Any kneading manners are applicable to the present
invention, for instance, all of the ingredients are pre-kneaded by
using a universal kneader and then kneaded by using a three roll
mill. The obtained composition is in the state of a paste. The
composition is applied to the alumina or beryllia ceramic substrate
by screen printing, and the printed pattern is dried at 120.degree.
C. for 10 to 15 minutes. The dried pattern is finally fired at a
temperature range of 850.degree. to 1060.degree. C. under nitrogen
atmosphere. The overall firing procedure extends over a period of
40 minutes, keeping the peak firing temperature for about 5 to
about 10 minutes.
The present invention is more specifically described and explained
by means of the following Examples, in which all % are by weight
unless otherwise noted. It is to be understood that the present
invention is not limited to the Examples, and various changes and
modifications may be made in the invention without departing from
the sprit and scope thereof.
REFERENCE EXAMPLE 1
There was reduced 4.0 l of an aqueous solution of copper sulfate
(concentration: 10%) with 150 g of glucose in the presence of 4 kg
of 5% NaOH at a temperature of 60.degree. C. for 30 minutes to give
a reaction mixture containing a precipitate of cuprous oxide. The
precipitate of cuprous oxide was separated from the reaction
mixture in an amount of 1.5 kg by decantation. There was dispersed
500 g of the obtained wet precipitate (squeezing ratio: 20%) in 0.5
l of water, and the mixture was reduced with 50 g of hydrazine at a
temperature of 50.degree. C. for 90 minutes. A copper powder is
separated from the reaction mixture in an amount of 80 g by
centrifugation. The obtained copper powder was washed with water,
dried and hydrogenated at a temperature of 230.degree. C. for 5
hours.
The obtained copper powder had an average particle size of 1.0
.mu.m, a tap density of 3.8 g/cm.sup.3 and an oxygen content of
0.10%.[Copper powder (A)].
REFERENCE EXAMPLE 2
The procedure of Reference Example 1 was repeated except that the
reduction temperature from copper sulfate to cuprous oxide was
altered from 60.degree. C. into 70.degree. C. to give a powder.
The obtained copper powder had an average particle size of 2.0
.mu.m, a tap density of 3.9 g/cm.sup.3 and an oxygen content of
0.12% [Copper powder (B)]
REFERENCE EXAMPLE 3
The procedure of Reference Example 1 was repeated except that the
squeezing ratio of cuprous oxide precipitate was altered from 20%
to 30%.
The obtained copper powder had an average particle size of 3.0
.mu.m, a tap density of 4.2 g/cm.sup.3 and an oxygen content of
0.13% [Copper powder (C)].
EXAMPLES 1 TO 6 AND COMPARATIVE EXAMPLES 1 and 2
A universal mixer was charged with a copper powder, a zinc oxide
powder, occasionally a nickel oxide powder, a glass powder and an
organic vehicle according to the formulation shown in Table 1, and
the mixture was pre-kneaded for 24 hours.
As the copper powder, five different copper powders having the
following properties were used.
______________________________________ Copper powder Designation
property A*.sup.1 B*.sup.2 C*.sup.3 D*.sup.4 E*.sup.5
______________________________________ Average particle 1.0 2.0 3.0
1.0 2.0 size (.mu.m) Tap density 3.8 3.9 4.2 3.7 3.8 (g/cm.sup.3)
Oxygen content 0.10 0.12 0.13 0.25 0.30 (%)
______________________________________ (Notes) *.sup.1 The copper
powder obtained in Reference Example 1 *.sup.2 The copper powder
obtained in Reference Example 2 *.sup.3 The copper powder obtained
in Reference Example 3 *.sup.4 Commercially available from Mitsui
Mining & Smelting Co., Ltd. under a trade name Cu Fine Powder
1110, lot No. S861009 PN *.sup.5 Commercially available from Mitsui
Mining & Smelting Co., Ltd. under a trade name Cu Fine Powder,
lot No. S861003 PNCS
As the glass powder, four different glass powders having the
following properties were used.
______________________________________ Glass powder Lead Zinc Lead
borate Designation borosilicate borosilicate composite property
(A)*.sup.1 (B)*.sup.2 (C)*.sup.3 glass (D)*.sup.4
______________________________________ Average 3.5 4.0 3.0 4.0
particle size (.mu.m) Softing 490 435 563 353 point (.degree.C.)
______________________________________ (Notes) All of the four
different glass powders were commercially available from Nippon
Denki Glass Kabushiki Kaisha. Trade names of the glass powders are
as follows: *.sup.1 GA-8 *.sup.2 GA-9 *.sup.3 GA-12 *.sup.4
LS-0803
The used zinc oxide powder was an extra pure reagent having an
average particle size of 0.7 .mu.m, which was commercially
available from Takeuchi Yakuhin Kabushiki Kaisha. The used nickel
oxide powder was an extra pure reagent having an average particle
size of 0.5 .mu.m, which was commercially available from Tokyo
Kasei Kabushiki Kaisha.
The used organic vehicle was a mixture of terpineol and ethyl
cellulose (100 cps) in a weight ratio of terpineol: ethyl
cellulose=95:5.
The composition was mixed by passing through a three roll mill
twelve times and then degassed in the universal mixer under in
vacuo to give a copper conductor composition in the state of a
paste. The obtained paste was applied to a 96% alumina substrate by
using a screen printer to give a printed pattern. The printed
pattern was dried at 120.degree. C. for 10 minutes by using a
hot-air dryer, and then fired in a belt conveyor furnace under a
nitrogen atomosphere for one cycle time of 40 minutes. The firing
profile was that the peak firing temperature was 900.degree. C.,
and the peak firing temperature was kept for 7 minutes. The firing
operation was repeated three times (three cycles).
With respect to the obtained conductor, the solderability and the
adhesion strength were measured. The results are shown in Table
2.
[Solderability]
After conducting screen-printing, the printed pattern is fired as
mentioned above to give a pattern (twenty 2 mm.times.2 mm
pads).
The pattern is dipped in XA-100, which is a tradename for solder
flux made by Tamura Kaken Kabushiki Kaisha, then is submerged in
the solder (60% Sn - 40% Pd) having a temperature of 250.degree. C.
for 5 seconds, and withdrawn. The withdrawn pattern is observed
with the naked eye.
.circle. : No pin hole.
.DELTA.: Pin holes were observed on 1 to 5 pads from among the 20
pads.
X: Pin holes were observed on 6 or more pads from among the 20
pads.
[Adhesion strength]
After conducting screen-printing, the printed pattern is fired, as
mentioned above to give a pattern (twenty 2 mm.times.2 mm
pads).
The pattern is dipped in XA-100, then is submerged in the solder
(60% Sn - 40% Pd) having a temperature of 250.degree. C. for 5
seconds, and withdrawn.
Tinned copper wire having a diameter of 0.8 mm.phi. were attached
to the 2 mm.times.2 mm pads by a soldering iron. As to the obtained
samples, the adhesive strength is measured by using a pull tester,
commercially available from Kabushiki Kaisha Shimdzu Seisakusho
under the tradename "Autograph", at a pull rate of 10 mm/min at the
time when copper thick film conductor is pulled off from the
substrate. The adhesive strength was measured before aging (initial
adhesive strength) and after aging the sample at 150.degree. C. for
250 hours (adhesive strength after heat-aging). The results shown
in Table 2 are averages of three samples, that is, 60 pads.
Initial adhesive strength
.circle. : Average value of 3 samples, 60 pads is 3.0 kg/4 mm.sup.2
or more
.DELTA.: Average value of 3 samples, 60 pads is from 2.5 kg/4
mm.sup.2 to less than 3.0 kg/4 mm.sup.2
X: Average value of 3 samples, 60 pads is less than 2.5 kg/4
mm.sup.2
Adhesive strength after heat-aging
.circle. : Average value of 3 samples, 60 pads is 2.0 kg/4 mm.sup.2
or more
.DELTA.: Average value of 3 samples, 60 pads is from 1.5 kg/4
mm.sup.2 to less than 2.0 kg/4 mm.sup.2
X : Average value of 3 samples, 60 pads is less than 1.5 kg/4
mm.sup.2
TABLE 1
__________________________________________________________________________
Amount of Amount of Amount of Copper powder zinc oxide nickel oxide
Glass powder organic vehicle Kind Amount (%) (%) (%) Kind Amount
(%) (%)
__________________________________________________________________________
Ex. No. (A) 3.0 1 (A) 75 1.0 -- 18.0 (D) 3.0 (A) 2.0 2 (B) 83 0.5
-- 12.0 (D) 2.5 (A) 3.0 3 (C) 82 1.0 -- 11.0 (D) 3.0 (A) 3.0 4 (A)
75 1.0 0.5 17.5 (B) 3.0 (C) 2.5 5 (B) 83 2.0 -- 11.0 (D) 1.5 (A)
1.5 6 (C) 74.5 1.5 -- 20.0 (D) 2.5 Com. Ex. (A) 3.0 1 (D) 82 1.0 --
11.0 (D) 3.0 (A) 3.0 2 (E) 82 1.0 -- 11.0 (D) 3.0
__________________________________________________________________________
TABLE 2 ______________________________________ Adhesive strength
(kg/mm.sup.2) Initial Adhesive strength Solderability adhesive
strength after heat-aging ______________________________________
Ex. No. 1 O O O 2 O O O 3 O O O 4 O O O 5 O O O 6 O O O Com. Ex. 1
.DELTA. .DELTA. X 2 .DELTA. .DELTA. X
______________________________________
As aforementioned, the copper conductor composition of the present
invention containing the copper powder having a low oxygen content
of 0.05 to 0.15% by weight can provide the copper conductor having
excellent solderability, adhesive strength and matching property to
resistances.
In addition to the ingredients used in the Examples, other
ingredients can be used in the Examples as set forth in the
specification to obtain substantially the same results.
* * * * *